HU207644B - Herbicide composition containing triazine- and pyrimidine-derivatives as active components and process for producing these compounds - Google Patents

Description

The present invention relates to a herbicidal agent containing a triazine or pyrimidine derivative as an active ingredient and to a process for their preparation.

In practice, a number of herbicidal and plant growth regulating pyrimidine and triazine derivatives are known.

No. 109,170 of the GDR patent discloses substituted pyrimidine derivatives which have growth regulating effects, for example, they promote root formation and growth, facilitate the peeling of fruit and promote dwarf growth.

Herbicidal compounds containing a 2,4,6-substituted 1,3,5-triazine ring are well known, for example, in British Patent 814,947, which discloses 6-chloro-1,3,5-triazine-2, United Kingdom Patent No. 1,132,306, which discloses 1,3-triazine-2,4-diamine derivatives substituted at the 6-position, wherein one of the amino groups is cyanoalkylamino. is substituted with.

Herbicidal and fungicidal 2-substituted 4,6-dichloro-1,3,5-triazine derivatives are described in H. Koopman et al .; Rec. Trav. Chim. 78, 967 (1959). About sixty-one compounds have been prepared and tested, including methyl 2- (4,6-dichloro-1,3,5-triazin-2-yl) oxy-2-methylacetic acid. According to the studies, the 2-alkoxy and 2-alkylthio-4,6-dichloro-1,3,5-triazine derivatives having 3 to 6 carbon atoms in the alkyl group are the most potent, and the corresponding and substituted alkyl compounds have the same effect. , while the 2-aryloxy and 2arylthiodichlorotriazines generally have no phytotoxic activity. In the field experiments, the 2-butoxy and 2-butylthiodichlorotriazine derivatives were first investigated, while the other related 2-alkoxy and 2-alkylthiochlorothriazine compounds were investigated in Rec. Trav. Chim. 79, 83, (1960).

EP 038 138 discloses the use of ethyl 2 - [(4-amino-6-methyl-1,3,5-triazin-2-yl) oxy] propionate with herbicidal sulfonamides, but with the triazine derivative and related compounds with no biological effect.

It has been found that the triazine or pyrimidine derivatives of the formula (I) substituted at the 2-position, wherein A is nitrogen or -CR ⁵ -, wherein R ⁵ is hydrogen,

R ¹ and R ² are each independently C 1-4 alkyl, C 1-4 alkoxy, halogen, C 1-4 alkylthio or C 1-4 mono or dialkylamino in alkyl,

R is a group of formula (a) wherein

R ³ is hydrogen, (C 1 -C 8) -alkyl, (C 1 -C 4) -alkylthioalkyl (C 3 -C 6) -cycloalkyl, thienyl (C 1 -C 6) -alkyl, alkyl (C 1 -C 6) 4 may be alkyl, C1-4 haloalkyl or C1-4 alkoxycarbonyl substituted and -COR ⁵ 'moiety wherein R ^5' is hydroxy, C1-4alkoxy, C1-4alkoxy a carbonyl group or a C 1-4 dialkylamino group in its alkyl moieties,

R ⁴ is -COR ⁶ , wherein

R ⁶ is hydroxy, C 2 -C 6 alkynyloxy, C 1 -C 8 alkoxy optionally substituted with halogen, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, optionally halogen, C 1 -C 4 alkyl, or Phenyl, thienyl, furanyl or tetrahydrofuranyl; and C1-C4 alkylthio, phenylthio, C14 dialkyliminoxy, or amino optionally substituted with 14 carbon atoms; or a phenyl group optionally substituted by C 1-4 alkyl or optionally substituted C 1-4 alkoxycarbonyl, optionally substituted by nitro, hydroxymethyl, C 1-4 alkyl or c) may be substituted with a group, or

R is a group of formula (b) wherein

R ⁴ 'is a carboxyl group or a C 1 -C 4 alkoxycarbonyl group,

R ⁹ is hydrogen,

^R10 is C1-4 alkyl, with the proviso that ^R? and / or ^R2 is other than chloro when A is a nitrogen atom, and these have an inorganic cation and an organic carboxylic acid salts have excellent herbicidal activity.

The alkyl or alkynyl group may be straight or branched, the alkyl group generally having from 1 to 8 carbon atoms, preferably from 1 to 6 carbon atoms, in particular from 1 to 4 carbon atoms. The alkynyl group generally has from 2 to 6 carbon atoms, preferably from 2 to 4 carbon atoms. Cycloalkyl is generally C3-C8.

Halogen is generally fluorine, chlorine or bromine.

The inorganic cation salts of the carboxylic acid salts of the compounds of formula I include alkali metals, alkaline earth metals such as sodium, potassium, calcium and magnesium, and transition metals such as copper, while the organic cations include alkylammonium or alkylsulfonium cations. The sodium salt is preferred as the carboxylic acid salt.

Preferred nitrogen is -CH-.

R ¹ and R ^{2 are} preferably halogen, C 1-4 alkyl, C 1-4 alkoxy,

A C4-C4 alkylthio group, a C1-C4 alkylamino group or a C1-C4 dialkylamino group in its alkyl moiety, including, in particular, chlorine, methyl, methoxy, methylthio, methylamino; or dimethylamino.

R is a group of formula (a) or (b). In the latter, one of R ⁹ and R ¹⁰ is hydrogen, the other is C 1 -C 4 alkyl, preferably methyl. Preferably R is -CHR ³ R ⁴ .

Preferably R ³ is C 1-6 alkyl, C 1-4 alkylthioalkyl, C 3-6 cycloalkyl, C 1-6 phenylalkyl, or phenyl. Particularly preferred R ³ is hydrogen, C 1-6 alkyl, C 1-4 alkylthioalkyl, cyclohexyl, benzyl, phenyl optionally substituted with one or more halo, C 1-4 alkyl or C 1-4 alkyl. substituted with an alkoxycarbonyl group, a thienyl group, a carboxyl group, a C 1 -C 4 alkoxycarbonyl group, a C 1 -C 4 alkoxycarbonylcarbonyl group, or a C 1 -C 4 dialkylcarbamoyl group in its alkyl moieties.

Preferably R ³ is C 2 -C 6 alkyl, in particular C 2 -C 4 alkyl, benzyl and unsubstituted phenyl, such as isopropyl, n-propyl, isobutyl, n-butyl, sec-butyl, tert-butyl, benzyl or phenyl.

Preferably R ⁴ is -COR ⁶ wherein R ⁶ is hydroxy, optionally substituted C 1-6 alkoxy, C 2-6 alkynyloxy, C 1-4 alkylthio, phenoxy, phenylthio, 1-4 dialkyliminoxy groups or amino groups.

R ⁴ is particularly preferably a group -COR ⁶ wherein R ⁶ is hydroxy, C1-4 alkoxy which can be substituted by halogen or C1-4 alkoxiesoporttal optionally, one C1 ^ alkylthio group, 1- C4 alkylthio, C2-4 alkynyloxy, phenoxy optionally substituted by one or more C1-4 alkyl, nitro or hydroxymethyl groups, phenylthio, amino, or an alkyl portion of a C 1-4 dialkylamino group. It may be substituted in the artificial portion of the phenoxy group represented by R ^{6 by} the group of formula (c).

R ⁴ is preferably within this group -COR ⁶ wherein R ⁶ is hydroxy or C 1-4 alkoxy.

Compounds of formula (I) other than hydrogen in R ³ contain asymmetric carbon atoms and may thus exist in various stereoisomeric forms. The scope encompasses the individual isomeric forms as well as any mixtures thereof. Thus, the R and S enantiomers of compounds of formula IA wherein R ³ is other than hydrogen and mixtures thereof.

The compounds of formula (I) may be prepared according to the invention if

a) a compound of formula (Π): wherein:

R ¹ , R ² and A are as defined above,

L is a leaving group, and is reacted with a compound of formula (ΙΠ)

R ³ and R ⁴ are as defined above, or

(b) reacting a compound of formula (IV) wherein A is -CR ⁵ - with a compound of formula (IV) wherein R ¹ , R ² and R ⁵ are as defined above, with a compound of formula (V) , in the formula

R ³ and R ⁴ are as defined above,

X is a leaving group and the resulting compound of formula (I) is optionally converted to another compound of formula (I) or the carboxylic acid of formula (I) is converted into a salt or the salt of the carboxylic acid of formula (I) into a free acid or other salt .

The leaving group may be any group which, under the reaction conditions, is cleaved from the starting material and thus promotes reaction at the appropriate site.

Preferably L is a halogen atom such as bromine, chlorine or iodine, and in the case of pyrimidine derivatives an alkanesulfonyl group such as methanesulfonyl group.

X is preferably a halogen atom or a sulfonyloxy group such as a methanesulfonyloxy group or a tosyloxy group. The halogen atom may be chlorine, bromine or iodine. Particularly preferred X is bromine.

Processes a) and b) are preferably carried out under alkaline conditions. For example, an alkali metal hybrid such as sodium or potassium hybrid, an alkaline earth metal hybrid such as calcium hybrid, an alkali metal carbonate or bicarbonate such as sodium or potassium carbonate or sodium bicarbonate, an alkali metal alkoxide, such as potassium tert-butoxide, an alkali metal hydroxide such as sodium or potassium hydroxide, or a tertiary amine such as triethylamine, pyrimidine or 1,8-diazabicyclo [5.4.0] undec-7-ene.

Processes a) and b) are preferably carried out in an inert organic solvent. Suitable solvents are, for example, hydrocarbons such as benzene or toluene, chlorinated hydrocarbons such as dichloromethane or chloroform, alcohols such as methanol or ethanol, ethers such as diethyl ether, tetrahydrofuran or 1,4-dioxane, ketones such as acetone or methyl ethyl ketone. esters such as ethyl acetate and aprotic polar solvents such as dimethylformamide, dimethylacetamide or dimethylsulfoxide; and nitriles such as acetonitrile or water, which are generally selected from the alkali used.

Processes (a) and (b) are suitable for the preparation of compounds of formula (I) having both groups in the meaning of R. R is represented by the general formula (b)

For the preparation of compounds having a needle group, R ³ is preferably a compound of formula (HI) or V containing an alkenyl group of formula -CR ⁹ R ¹⁰ - wherein R ⁹ is hydrogen and R ¹⁰ is 1-. C4 alkyl. In this case, no additional hydrogen atom is present on the carbon bearing R ³ .

The two processes may be carried out at a wide reaction temperature, for example between O'C and the boiling point of the reaction mixture.

The amount of starting material (II) and (IH) can be varied within wide limits, preferably from 0.1 to 10 moles of compound (Π) per mole of compound (ΠΓ). Within this, the starting compounds are preferably used in equimolar amounts.

Likewise, the amount of compounds of formulas IV and V can be varied within wide limits, preferably 0.1 to 10 moles of compound of formula IV are used per mole of compound of formula V, preferably in equimolar amounts.

The enantiomers of formula (I) may be prepared using the corresponding optically active enantiomer of formula (IH) or formula (V) or by resolution of the resulting optical isomer mixture. In the preparation of enantiomers of formula (I) ^R3 is appropriate aryl is preferably used in an optically active (ΠΙ) or formula (V) acid, i.e., where R ⁴ is -COOH, and the resulting optically active (I) of formula if desired, the compound is converted to the corresponding ester derivative.

The compounds of formula (I) obtained by process (a) or (b) may, if desired, be converted into other compounds of formula (I) by methods known to those skilled in the art. For example, compounds of formula (I) wherein R ¹ and / or R ^{2 are} halogen atoms, preferably chlorine, are reacted with nucleophilic compounds, for example, by reaction with an amine such as dimethylamine to form an amino group of R ¹ and / or R ² m.p. The compounds of formula I wherein R ¹ and / or R ^{2 are} halogen are furthermore provided with an organometallic compound containing an alkylthio group, such as sodium methane thiolate, for a corresponding R ¹ and / or R ² alkylthio group such as methylthio. can be converted to a compound of formula (I) or hydrogenated to a compound of formula (I) wherein R ¹ and / or R ² are hydrogen. Compounds of formula (I) wherein R ⁴ is ester may be hydrolyzed to the corresponding acid in conventional manner. Alternatively, the corresponding ester such as benzyl ester may be hydrogenated to produce the acid of formula (I).

The acid-salt conversion is carried out in the usual manner.

The resulting compounds of formula (I) may, if desired, be isolated and purified in conventional manner.

The triazine derivatives of the formula (Π) used as starting materials, i.e. the compounds of the formula (Π) in which A is nitrogen, are known or can be prepared in a conventional manner. For example, these compounds may be prepared from 2,4,6-trichlorotriazine (Dudley et al., J. Am. Chem. Soc., 73, 2986, 1951); Koopman et al., Rec. Trav. Chim., 79, 83, (1960); Hirt et al., Helv. Chim. Acta, 33, 1365 (1950); Köbe et al., Monatshefte für Chemie, 101, 724 (1970) and Ross et al., U.S. Patent 3,316,263.

The pyrimidine derivatives of Formulas (Π) and (IV) may be prepared by conventional means (Heterocyclic Compounds, 16, "The Pyrimidines", D. J. Brown, Interscience, 1962).

The starting materials of the formula (ΙΠ) are known or can be prepared in a conventional manner. Compounds containing an aryl group represented by R may be prepared for example, if the aldehyde corresponding R ³ CHO is reacted with cyanide such as potassium cyanide or trimethylsilyl cyanide, followed by treatment with zinc iodide or sodium biszulfiddal, and the cyano group is converted into R ⁴ group [Schnur and Morville, J. Med. Chem. 29, 770 (1986); U.S. Patent 4,537,623]. For example, compounds containing an alkyl group at R ³ may be prepared starting from the corresponding amino acid in two steps [Kolasa and Miller, J. Org. Chem., 52, 4978 (1987)].

Compounds of formula (V) may be prepared in conventional manner, for example by halogenation of the corresponding compound (Epstein et al., J. Med. Chem., 1981, 24, 481).

The compounds of the formula I have a strong herbicidal action, including a broad pre- and post-emergence action against undesirable weeds.

The herbicidal compositions according to the invention contain, in addition to the active ingredient of the formula I, a suitable carrier and, if desired, a surfactant.

In use, the herbicidal composition of the invention is applied to the habitat of the treated weed, i.e. to the plant or soil.

The application rate of the new active compound is generally 0.01 to 10 kg / ha, preferably 0.05 to 4 kg / ha.

The carrier of the compositions of the present invention may be any material which can be used to convert the active ingredient into a suitable formulation. Solid or liquid materials, such as liquefied gases, are also preferably used as carriers.

The composition according to the invention preferably contains 0.595% by weight of the active ingredient.

Solid carriers include natural and synthetic materials and silicates such as natural silicates such as diatomaceous earth, magnesium silicate such as talc, magnesium aluminum silicate such as attapulgite and vermiculite, aluminosilicate such as kaolinite, montmorillonite, and mica carbonate, sulfate, ammonium sulfate, synthetic hydrate silicon oxides and synthetic calcium or aluminum silicates, suitable elements such as carbon or sulfur, natural or synthetic resins such as coumarins, polyvinyl chloride and styrene polymers and copolymers, solid polychlorophenols,

644 Β bitumen, waxes, and solid fertilizers such as superphosphate.

Suitable liquid carriers are water, alcohols such as isopropanol and glycol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ether, aromatic and araliphatic hydrocarbons such as benzene, toluene and xylene, petroleum fractions such as kerosene and light petroleum, chlorinated hydrocarbons such as carbon tetrachloride, perchlorethylene and trichloroethane, and mixtures thereof.

The agricultural composition is often formulated in concentrated form and transported to the site of use, where it is diluted to a suitable concentration before use. A surfactant is used as an additional additive to accelerate the dilution process.

Suitable surfactants are emulsifiers, dispersants and wetting agents, preferably nonionic or ionic surfactants. Examples include sodium or calcium salts of polyacrylic acid, sodium or calcium salts of lignite sulphonic acids, fatty acids or aliphatic amines or amides with ethylene oxide and / or propylene oxide condensates containing at least 12 carbon atoms, glycerol, sorbitol ester and sucrose , condensates thereof with ethylene oxide and / or propylene oxide, condensates with fatty alcohol or alkylphenol such as p-octylphenol or p-octylcresol with ethylene oxide and / or propylene oxide, sulphates or sulphonates of condensed products, preferably alkaline or alkaline earths, sodium salts of sulfuric or sulfonic acid esters, such as sodium lauryl sulfate, sodium secondary alkyl sulfate, sodium salt of sulfonated castor oil, and sodium salts of alkylarylsulfonates such as dodecylbenzene sulfonate and ethylene oxide,

Further herbicidal, fungicidal or insecticidal agents may be incorporated into the composition of the invention if desired.

The following examples illustrate the present invention, but are not intended to limit the scope thereof.

Example I

Methyl 2- (4,6-dimethyl-pyrimidin-2-yl) oxy-3-methylbutanoate

a) 2-Acetoxy-3-methylbutanoic acid

11.7 g (0.1 mol) of dlvaline are mixed in 300 ml of glacial acetic acid. While stirring, 13.8 g of sodium nitrite are added over one hour while the reaction mixture is kept on a water bath at room temperature. The reaction mixture was then stirred overnight at room temperature, the acetic acid was removed and the residue was treated with 50 ml of water. After extraction with diethyl ether, the organic phase is washed with water, dried over anhydrous magnesium sulfate and the ether is evaporated. 12.2 g of the title compound are obtained in the form of a colorless oil.

b) Methyl 2-hydroxy-3-methylbutanoate

II, 2 g (0.09 mol) of product (a) is taken up in 160 ml of absolute methanol and cooled to -40 ° C. Thionyl chloride (5.7 mL, 0.099 mol) was added with stirring at this temperature for 30 minutes and then allowed to warm to room temperature overnight. Evaporation to dryness gave 7.7 g (65%) of the title compound as an oil.

c) Methyl 2- (4,6-dimethylpyrimidin-2-yl) oxy-3-methylbutanoate

1.5 g of the product of b) and 2.11 g (0.011 mol) of 4,6-dimethyl-2-methanesulfonylpyrimidine are dissolved in 20 ml of acetone. 1.6 Potassium carbonate was added and refluxed for 4 hours. The progress of the reaction was monitored by TLC, evaporated to dryness and taken up in 10 mL of water. The mixture was extracted with chloroform, dried over anhydrous sodium sulfate and the solvent removed. The oily residue was purified by flash chromatography (1: 1 ethyl acetate: hexane) to give 1.1 g (42%) of the title compound as a colorless oil.

Elemalanízis:

H, 7.6; N, 11.8. Found: C, 60.3; H, 7.9; N, 11.7%.

NMR (CDCl ₃ , δ ppm): 6.65 (1H, s), 5.01 (1H, d), 3.7 (3H, s), 2.46 (6H, s), 2.40 (1H , m), 1.10 (6H, dd).

Example 2

2- (4,6-Dimethyl-pyrimidin-2-yl) oxy-3-methylbutanoic acid

The butanoate of Example 1 (0.8 g, 3.36 mmol) was dissolved in absolute methanol (8 mL) and treated with 10% aqueous sodium hydroxide (8 mL). The reaction mixture was stirred overnight at room temperature, during which the progress of the reaction was monitored by TLC. The methanol was removed and the residue was mixed with 5 mL of water. After cooling, the reaction mixture was adjusted to pH 2 with concentrated hydrochloric acid and extracted twice with chloroform. The extract was dried over anhydrous sodium sulfate and evaporated. The resulting 0.7 g of an oily solid was triturated with 5 mL of diethyl ether to give 0.5 g (66%) of a colorless solid. Melting point: 131.8 ° C.

ANALYSIS:

Calculated: C, 58.9; H, 7.1; N, 12.5; Found: C, 59.1; H, 7.2; N, 12.7.

Example 3

Methyl 2- (4,6-dimethoxypyrimidin-2-yl) oxy-2-phenylacetate

4.3 g (20 mmol) of 4,6-dimethoxy-2-methanesulfonylpyrimidine, 3.3 g (20 mmol) of mandelic acid methyl ester and 2.76 g (20 mmol) of potassium carbonate in 100 ml of methyl ethyl ketone the mixture is refluxed for 3 hours. After evaporation of the solvent, the residue was diluted with 200 mL of water and the activating precipitate was filtered and dried. 5.02 g (83%) of the title compound are obtained. Melting point: 100.6 ° C.

ANALYSIS:

H, 5.3%; N, 9.2%. Found: C, 58.6; H, 5.3%; N, 9.3%.

HU 207 644 Β

Example 4

2- (4,6-dimethoxypyrimidin-2-yl) oxy-2-phenylacetic acid

A mixture of the compound of Example 3 (1.22 g, 4 mmol) and sodium hydroxide (0.16 g, 4 mmol) in methanol (20 mL) was stirred for 2 hours at 0 ° C and overnight at room temperature. The progress of the reaction was monitored by TLC. The methanol was evaporated in vacuo, the residue was diluted with water (50 mL), the aqueous phase was slightly acidified with dilute hydrochloric acid, and the precipitate was filtered off and dried. Recrystallization from ethyl acetate / hexane gave 0.65 g (56%) of the title compound. Melting point: 159.0 ° C.

ANALYSIS:

H, 4.8; N, 9.7. Found: C, 58.4; H, 4.9; N, 10.0%.

Example 5

Methyl 2- (4,6-dimetaxi -], 3,5-triazin-2-yl) oxy-3-methylbutanoate

2.00 g (0.011 mol) of 2-chloro-4,6-dimethoxytriazine, 1.5 g of methyl 2-hydroxy-3-methylbutanoate, 1.73 g (0.013 mol) of potassium carbonate and 50 ml the mixture of methyl ethyl ketone was refluxed overnight. The reaction was monitored by TLC followed by filtration of the sodium carbonate and removal of the solvent. This gives 2.38 g of a yellow solid which is purified by flash chromatography. This gave 1.93 g (65%) of the title compound as a pale yellow oil.

ANALYSIS:

Calc'd: C, 48.7; H, 6.3; N, 15.5; Found: C, 47.1; H, 5.8; N, 17.0.

NMR (CDCl ₃ , δ ppm): 5.08 (1H, d), 3.98 (6H, s), 3.72 (3H, s), 2.30 (1H, m), 1.07 (6H) , dd).

Example 6

Ethyl 2- (4,6-triazin-2-yl) oxy-2-phenylacetate

A mixture of 1.75 g of 2-chloro-4,6-dimethoxytriazine, 1.8 g of mandelic acid ethyl ester and 1.5 g of potassium carbonate in 75 ml of methylethylketone is stirred at reflux overnight. The reaction mixture was cooled to room temperature, concentrated and the residue was poured into water. The precipitate was filtered off, washed with water and dried. 2.6 g (81.5%) of the title compound are obtained. Melting point: 92 ° C.

ANALYSIS:

H, 5.4%; N, 13.2%. Found: C, 57.0; H, 5.4%; N, 13.0%.

Example 7

Ethyl 2- (4,6-dimethylpyrimidin-2-yl) oxyacetate g (0.08 mol) of 2-hydroxy-4,6-dimethylpyrimidine was dissolved in 150 ml of dimethylformamide and Ethyl bromoacetate (0.08 mol) was added followed by potassium carbonate (11.1 g). After refluxing overnight, the precipitate is filtered off, the solvent is removed from the filtrate, and the crude oil obtained is purified by flash chromatography. 4.5 g of the title compound are obtained in the form of a red oil.

ANALYSIS:

H, 6.7; N, 13.3; Found: C, 56.9; H, 6.9; N, 13.0;

NMR (CDCl ₃ δ ppm): 6.68 (1H, s), 4.87 (2H, s), 4.20 (2H, q), 2.37 (6H, s), 1.22 (3H, t).

Example 8

2- (4,6-Dimethyl-pyrimidin-2-yl) -oxy-acetic acid Example 7 Ethyl ester (9.5 mmol) was dissolved in ethanol (20 mL). 25 ml of 10% aqueous sodium hydroxide solution are added and the mixture is refluxed for 4 hours. The reaction was monitored by TLC and the ethanol was removed, the aqueous residue was cooled, adjusted to Ph = 2, and the product was extracted with chloroform. The extract was dried over anhydrous sodium sulfate and evaporated to give 0.6 g (35%) of the title compound as a reddish oil which crystallized on standing. Melting point: 72 “C.

ANALYSIS:

Calculated: C, 52.7; H, 5.5; N, 15.4; Found: C, 48.6; H, 5.6; N, 13.4;

NME (CDCl ₃ , δ ppm): 6.70 (1H, s), 6.51 (1H, broad s),

4.93 (2H, s), 2.48 (6H, s).

Example 9

Ethyl 2- (4,6-dimethyl-pirimiditi-2-yl) -2-phenylacetate

5.60 g (50 mmol) of 2-hydroxy-4,6-dimethylpyrimidine, 12.15 g (50 mmol) of ethyl 2-bromo-2-phenylacetate and 6.90 g (50 mmol) of potassium carbonate 250 of methylethylketone was refluxed overnight. The solvent was removed and the residue was mixed with water and extracted with diethyl ether. The extract was dried over anhydrous magnesium sulfate and evaporated. The crude product was purified by flash chromatography to give 4.8 g (34%) of the title compound as an oil.

ANALYSIS:

Calculated: C, 67.1; H, 6.3; N, 9.8; Found: C, 67.4; H, 6.5; N, 9.4.

Example 10

2- (4,6-Dimethyl-pyrimidin-2-yl) oxy-2-phenylacetic acid

3.60 g (12 mmol) of the ethyl ester of Example 9 are added to a solution of 0.504 g (12.6 mmol) of sodium hydroxide in 20 mL of ethanol and 20 mL of water, cooled to 0 ° C and stirred. The reaction mixture was stirred at this temperature for 2 to 3 hours, then allowed to gradually warm to room temperature and stirred overnight. The reaction mixture was diluted with water (about 300 ml), acidified slightly with hydrochloric acid, and the precipitate was filtered off and dried. Recrystallization from hexane / ethyl acetate gave 2.4 g (74%) of the title compound. Melting point; 148.4 ° C.

ANALYSIS:

H, 5.4%; N, 10.9%. Found: C, 64.7; H, 5.5%; N, 11.5%.

HU 207 644 Β

Example 11

2- (4,6-Dimethoxy-triazin-2-yl) -oxy-2-phenyl-acetic acid 1.22 g (4.0 mmol) of methyl 2- (4,6-dimethoxy-triazin-2-yl) -oxy -2-Phenylacetate (preparation analogous to the ethyl ester described in Example 6) was added to a stirred solution of 0.16 g (4.0 mmol) of sodium hydroxide in 20 mL of water and 20 mL of ethanol. The reaction mixture is heated at reflux for 1 hour, during which time the reaction is monitored by TLC. The methanol was evaporated in vacuo (10), the residue was diluted with water (50 mL), and the resulting precipitate was filtered, washed and dried. 0.73 g (63%) of the title compound is obtained. 128.2 ° C.

ANALYSIS:

H, 4.5%; N, 14.4%. Found: C, 53.2; H, 4.6; N, 14.5%.

12-163. examples

1-11. The following compounds of the general formula (Ta) can be prepared according to the following Examples. Exceptions to paragraphs 159-162. EXAMPLE 1b Starting from benzyl ester (Examples 155-158) which is hydrogenated at ambient temperature with palladium on carbon in the presence of ethanol at room temperature.

Table 1

Example- song THE R ¹ R ² R ³ R ⁴ Op. ( "C) Elemental Analysis (Calculated, Found) C H N 12 N OCH ₃ and ₃ c ₆ h ₅ CO ₂ CH ₃ 91.5 55.1 4.9 13.8 55.5 4.9 13.8 13 CH ch ₃ ch ₃ 2-H ₄ C1c _his co ₂ c ₂ h ₅ 72-75 59.9 5.3 8.7 58.9 5.2 8.4 14 N and ₃ and ₃ 2-FC ₆ H ₄ co ₂ ch ₃ 93 52.0 4.4 13.0 51.5 4.6 12.2 15 CH and ₃ and ₃ 2-FC ₆ H ₄ co ₂ ch ₃ 90-92 55.9 4.7 8.7 56.0 4.8 8.6 16 N and ₃ and ₃ 3-CF ₃ C ₆ H ₄ co ₂ ch ₃ oil 48.3 3.8 11.3 48.7 4.0 11.1 17 CH and ₃ and ₃ 3-CF ₃ C ₆ H ₄ co ₂ ch ₃ 96-99 51.6 4.1 7.5 51.5 4.1 7.7 18 CH ch ₃ ch ₃ 2- (CO ₂ CH ₃ ) C ₆ H ₄ co ₂ ch ₃ oil 61.8 5.5 - 61.2 5.7 - 19 CH and ₃ and ₃ 2,6-diClC ₆ H ₃ co ₂ ch ₃ 169-170 48.3 3.8 7.5 48.7 3.9 7.4 20 CH and ₃ and ₃ ch ₂ c ₆ h ₅ co ₂ ch ₃ oil 60.4 5.7 8.8 60.3 5.8 8.7 21 N and ₃ and ₃ ch ₂ c ₆ h ₅ co ₂ ch ₃ oil 56.4 5.4 13.2 56.4 5.5 12.8 22 CH and ₃ and ₃ ch ₂ c ₆ h ₅ COOH 113.5 59.3 5.3 9.2 58.4 5.3 9.1 23 N and ₃ cl ch ₂ c ₆ h _s co ₂ ch ₃ oil 51.9 4.3 13.0 51.3 4.4 12.9 24 N and ₃ N (CH ₃ ) ₂ ch ₂ c ₆ h ₅ co ₂ ch ₃ 61-62 57.8 6.0 16.9 58.2 6.0 17.1 25 N and ₃ nhch ₃ ch ₂ c ₆ h ₅ co ₂ ch ₃ 62-64 56.6 5.7 17.6 56.0 5.7 17.8 26 N and ₃ sch ₃ ch ₂ c ₆ h ₅ co ₂ ch ₃ - oil 53.7 5.1 12.5 - - -

HU 207 644 Β

Example- song THE R ¹ R ² R ³ R ⁴ Op. (° C) Elemental Analysis (Calculated, Found) C H N 27 CH cl OCH ₃ QH ₅ CO ₂ CH ₃ 72.4 54.5 4.2 9.1 54.7 4.3 9.3 28 CH OCH ₃ sch ₃ c ₆ h ₅ co ₂ ch ₃ 93.95 56.2 5.0 8.7 55.8 5.1 9.1 29 CH and ₃ and ₃ co ₂ ch ₃ 118-120 50.3 4.6 9.0 50.4 4.6 8.8 30 CH ch ₃ and ₃ c ₆ h ₅ co ₂ ch ₃ 70.7 62.5 5.6 9.7 62.8 5.7 9.7 31 CH and ₃ and ₃ c ₆ h ₅ COOH (S) 137-140 57.9 4.9 9.7 57.5 5.0 9.5 32 CH and ₃ and ₃ c ₆ h ₅ COOH (R) 133 57.9 4.9 9.7 58.1 5.1 10.0 33 CH and ₃ and ₃ c ₆ h ₅ CO _z CH ₃ (S) 95 59.2 5.3 9.2 59.0 5.3 9.1 34 CH and ₃ and ₃ c ₆ h ₅ CO ₂ CH ₃ (R) 92-94 59.2 5.3 9.2 59.4 5.4 9.1 35 CH ch ₃ ch ₃ c ₆ h ₅ co ₂ ch ₃ 68.2 66.2 5.9 10.3 66.3 6.1 10.1 36 N and ₃ N (CH ₃ ) ₂ c ₆ h ₅ co ₂ ch ₃ 103.5 56.6 5.7 17.6 56.7 5.8 17.5 37 CH and ₃ and ₃ c ₆ h ₅ COCTNa ⁺ 242-243 53.9 4.2 9.0 52.4 4.3 8.9 38 N and ₃ nhch ₃ c ₆ h ₅ co ₂ ch ₃ 112.2 55.3 5.3 18.4 55.6 5.5 18.1 39 N N (CH ₃ ) ₂ ch ₃ c ₆ h ₅ co ₂ ch ₃ 133.2 59.6 6.0 18.5 59.4 6.0 18.4 40 N ch ₃ and ₃ C ₆ H ₅ co ₂ ch ₃ 72 58.1 5.2 14.5 59.0 5.2 14.7 41 CH ch ₃ ch ₃ ch ₃ co ₂ ch ₃ oil 57.1 6.7 13.3 - - - 42 CH ch ₃ ch ₃ ch ₃ COOH 117 55.1 6.1 14.3 46.5 6.3 14.3 43 CH ch ₃ ch ₃ c ₂ h ₅ CO ₂ CH ₃ oil 58.9 7.1 12.5 58.7 7.2 12.0 44 CH ch ₃ ch ₃ c ₂ h ₅ COOH 112.5 57.1 6.7 13.3 57.1 6.8 13.1 45 CH CH3 ch ₃ ÍC4H9 CO ₂ CH ₃ oil 61.9 7.9 11.1 63.3 8.3 10.7 46 CH ch ₃ ch ₃ ÍC4H9 COOH 111.9 60.5 7.6 11.8 59.7 7.5 12.2 47 CH ch ₃ ch ₃ SC4H9 CO ₂ CH ₃ , oil 61.9 7.9 11.1 58.9 7.8 9.7

HU 207 644 Β

Example- song THE R ¹ R ² R ³ R ⁴ Op. (° C) Elemental Analysis (Calculated, Found) C H N 48 CH ch ₃ ch ₃ sc ₄ h ₉ COOH 115.0 60.5 7.6 11.8 60.9 8.0 11.1 49 CH ch ₃ ch ₃ nC ₃ H ₇ CO ₂ CH ₃ oil 60.5 7.5 11.8 58.8 7.4 11.2 50 CH ch ₃ ch ₃ TCz ^ hij co ₂ ch ₃ oil 61.9 7.9 11.1 59.2 8.0 10.1 51 CH ch ₃ ch ₃ 11C4H9 co ₂ ch ₃ oil 61.9 7.9 11.1 - - - 52 CH and ₃ and ₃ CH ₃ COOH 144 47.4 5.3 12.3 44.4 4.9 12.5 53 CH and ₃ and ₃ c ₂ h ₅ COOH 122 49.6 5.8 11.6 47.6 5.9 11.1 54 CH and ₃ and ₃ íc ₃ h ₇ COOH 133.5 51.6 6.3 10.9 51.6 6.2 11.1 55 CH and ₃ and ₃ ÍC4H9 CO ₂ CH ₃ oil 54.9 7.0 9.9 55.0 7.1 10.0 56 CH and ₃ and ₃ iC ₃ H ₇ co ₂ ch ₃ 48.4 53.3 6.7 10.4 53.8 7.1 10.8 57 CH and ₃ and ₃ ÍC4H9 COOH 116 53.3 6.7 10.4 52.9 6.7 10.4 58 CH and ₃ and ₃ SC4H9 CO ₂ CH ₃ 42 54.9 7.0 9.9 54.8 7.5 9.5 59 CH and ₃ and ₃ SC4H9 COOH 96.2 53.3 6.7 10.4 53.9 6.9 10.5 60 CH and ₃ and ₃ I1C3H7 CO ₂ CH ₃ 60.5 53.3 6.7 10.4 53.3 6.8 10.4 61 CH and ₃ and ₃ I1C3H7 COOH 114 51.6 6.3 10.9 51.5 6.5 10.7 62 CH and ₃ and ₃ tC ₄ H9 CO ₂ CH ₃ 104.5 54.9 7.0 9.9 54.4 6.9 9.6 63 N and ₃ and ₃ ch ₃ CO ₂ CH ₃ (R) oil 44.4 5.3 17.3 44.5 5.4 17.8 64 N and ₃ and ₃ ch ₃ CO ₂ CH ₃ (S) oil 44.4 5.3 17.3 45.4 5.6 16.9 65 N and ₃ and ₃ C ₂ H _s co ₂ ch ₃ oil 46.7 5.8 16.3 44.6 5.6 14.8 66 N and ₃ and ₃ 1C4H9 co ₂ ch ₃ oil 50.5 6.7 14.7 51.5 7.0 11.8 67 N and ₃ and ₃ nC ₃ H ₇ co ₂ ch ₃ oil 48.7 6.3 15.5 48.8 6.7 15.4 68 CH and ₃ and ₃ tC ₄ H9 COOH, 167.5 53.3 6.7 10.4 53.2 6.8 10.5

HU 207 644 Β

Example- song THE R ¹ R ² R ³ R ⁴ Op. co Elemental Analysis (Calculated, Found) C H N 69 CH and ₃ and ₃ nC ₄ H ₉ co ₂ ch ₃ oil 54.9 7.0 9.9 51.3 6.6 9.4 70 CH and ₃ and ₃ T1C4H9 COOH 113.7 53.3 6.7 10.4 53.6 6.7 10.4 71 CH and ₃ and ₃ 3-CH ₃ C ₆ H ₄ CO ₂ CH ₃ 122.8 60.4 5.7 8.8 59.7 5.7 9.4 72 CH and ₃ and ₃ 4-CH ₃ C ₆ H ₄ COCH3 113.8 60.4 5.7 8.8 60.7 6.0 8.9 73 CH and ₃ N (CH ₃ ) ₂ c ₆ h ₃ co ₂ ch ₃ 94.1 60.6 6.0 13.2 60.6 5.9 13.3 74 CH and ₃ and ₃ 2,6-diClCl3 ₃ COOH 246.6 46.8 3.4 7.8 47.1 3.4 8.0 75 N and ₃ and ₃ C ₆ H _S CO ₂ CH ₃ (R) 95.0 55.1 5.0 13.8 55.7 5.0 13.7 76 N and ₃ and ₃ c ₆ h ₅ CO ₂ CH ₃ (S) 98.0 55.1 5.0 13.8 55.1 5.0 14.4 77 N and ₃ and ₃ SHE co ₂ ch ₃ 67.3 46.3 4.2 13.5 46.4 4.1 13.2 78 CH and ₃ and ₃ iC ₃ H ₇ COCTNA ⁺ 196.1 47.5 5.4 10.1 46.5 5.4 9.9 79 CH and ₃ and ₃ C ₃ H ₇ co ₂ ch ₃ (S) 41.0 53.3 5.7 10.4 54.2 6.6 10.5 80 CH and ₃ and ₃ ÍC3H7 co ₂ ch ₃ 47.0 53.3 6.7 10.4 53.4 7.1 9.9 81 CH and ₃ and ₃ iC ₃ H ₇ co ₂ c ₂ h ₅ 45.5 to 46.0 54.9 7.0 9.9 53.5 6.9 9.7 82 CH and ₃ and ₃ C ₃ H ₇ CO2ÍC3H7 46.0 to 46.5 56.4 7.0 9.9 56.3 7.2 9.7 83 CH and ₃ and ₃ C ₃ H ₇ CO2T1C4H9 41.5 to 42.0 57.7 7.7 9.0 56.9 7.2 8.7 84 CH and ₃ and ₃ nC ₆ H, ₃ COOH 105.6 56.4 7.4 9.4 56.8 7.6 8.7 85 CH and ₃ and ₃ cyclohexyl COOH (R) 162.5 56.7 6.8 9.5 55.6 6.7 9.4 86 CH and ₃ and ₃ cyclohexyl COOH (S) 152.0 56.7 6.8 , ⁹ ' ⁵ 55.7 6.8 8.9 87 CH and ₃ and ₃ (CH2) ₂ SCH ₃ COOH 85.6 45.8 5.6 9.7 44.5 5.5 9.5 88 CH and ₃ and ₃ coco ₂ ch ₃ CO ₂ CH ₃ 98.0 45.9 4.5 8.9 43.5 5.0 8.1

HU 207 644 Β

Example- song THE R ¹ R ² R ³ R ⁴ Op. CC) Elemental Analysis (Calculated, Found) C H N 89 CH and ₃ and ₃ CON (CH ₃ ) ₂ CO ₂ CH ₃ 133,0- 134.0 48.2 5.7 14.0 47.9 5.7 13.5 ' 90 CH and ₃ and ₃ íc ₃ h ₇ CO ₂ (CH ₂ ) ₂ OC ₂ H ₅ 46.4 54.9 7.3 8.5 55.1 8.2 8.4 91 CH and ₃ and ₃ C ₃ H ₇ CO ₂ N = C (CH ₃ ) ₂ oil 54.0 6.8 13.5 54.3 6.8 13.5 92 CH and ₃ and ₃ C ₃ H ₇ co ₂ ch ₂ - / _s 2 115.2 54.5 5.7 8.0 54.1 5.9 7.7 93 CH and ₃ and ₃ íc ₃ h ₇ CO ₂ CH ₂ C ₆ H ₅ 78.0 62.4 6.4 8.1 62.3 6.5 8.4 94 CH and ₃ and ₃ C ₃ H ₇ CO ₂ CH ₂ CsCH 75.7 57.1 6.1 9.5 57.4 6.8 9.9 95 CH and ₃ and ₃ C ₃ H ₇ ^ CH, 80.6 62.4 6.4 8.1 62.2 6.9 8.4 96 CH and ₃ and ₃ C ₃ H ₇ CO2ÍC4H9 43.0 57.7 7.7 8.9 57.8 8.1 9.3 97 CH and ₃ and ₃ íc ₃ h ₇ COSnC ₃ H ₇ 52.2 53.5 7.0 8.9 53.8 7.2 9.1 98 CH and ₃ and ₃ C ₃ H ₇ COSC ₆ H ₅ 130.7 58.6 5.7 8.0 58.5 5.9 8.3 99 CH and ₃ and ₃ C ₃ H ₇ CO2SC4H9 43.1 57.7 7.7 8.9 57.5 7.5 8.9 100 CH and ₃ and ₃ C ₃ H ₇ CO ₂ CH (CH ₃ ) C ₆ H ₅ oil 63.3 6.7 7.8 63.3 6.5 8.0 101 CH and ₃ and ₃ ÍC ₃ H ₇ CO ₂ (CH ₂ ) ₂ SCH ₃ 47.9 50.9 6.7 8.5 51.1 6.4 8.6 102 CH and ₃ and ₃ C ₃ H ₇ CO ₂ (CH ₂ ) ₂ Cl 38.5 48.9 6.0 9.3 49.3 6.1 8.8 103 CH and ₃ and ₃ íc ₃ h ₇ co ₂ ch ₂ 110.6 57.1 5.9 8.3 56.8 6.2 9.0 104 CH and ₃ and ₃ íc ₃ h ₇ CO ₂ CH ₂ \ ^x 0 ⁷ oil 56.5 7.1 8.2 56.8 7.1 8.5 105 CH and ₃ and ₃ C ₃ H ₇ ck CO ₂ CH ₂ - {/ - Cl 110.4 52.0 4.8 6.7 ¹ 52.1 5.0 6.4

HU 207 644 Β 2

Example- song THE R ¹ R ² R ³ R ⁴ Op. (° C) Elemental Analysis (Calculated, Found) C H N 106 CH OCH ₃ and ₃ íc ₃ h ₇ CO ₂ CH ₂ _θ- Cl 92.9 56.8 5.5 7.4 56.5 5.6 6.9 107 CH and ₃ and ₃ íc ₃ h ₇ co ₂ ch ₂ ^och 3 oil 60.6 6.4 7.4 60.0 5.9 7.3 108 CH and ₃ and ₃ íc ₃ h ₇ CONHN (CH ₃ ) ₂ 130.8 52.3 7.4 18.8 52.2 7.9 18.9 109 CH and ₃ and ₃ iC ₃ H ₇ OCH, co ₂ ch ₂ 49.0 60.6 6.4 7.4 60.0 5.9 7.3 110 CH and ₃ and ₃ C ₃ H ₇ CONHNH ₂ 178.1 48.9 6.7 20.7 49.1 6.8 19.9 111 CH and ₃ and ₃ 1C ₃ H _v CONH - CO, CH 98.0 58.6 5.9 10.8 58.1 6.0 10.5 112 CH and ₃ and ₃ íc ₃ h ₇ ^c ° ² 172.6 54.1 5.0 11.1 54.6 5.3 11.1 113 CH and ₃ and ₃ íc ₃ h ₇ ^cOjH Q TH ₂ OH oil 59.7 6.1 7.7 60.3 6.5 7.0 114 CH and ₃ and ₃ íc ₃ h ₇ ^C ^ o / Uh / n ^<och 'HCOCCO, ^{1}> n} -% CH OCH CH, Z \ H, C CH, 130.3 58.0 6.0 9.3 57.4 5.8 8.8 115 CH and ₃ och tC ^ Hg CO ₂ CH ₂ C = CH 95.0 58.6 6.5 9.1 58.4 6.5 9.0 116 CH and ₃ and ₃ tC ^ Hg COSnC ₃ H ₇ 76.0 54.9 7.3 8.5 55.7 7.4 8.8 117 CH and ₃ and ₃ tC ^ Hg CO ₂ N = C (CH ₃ ) ₂ oil 55.4 7.1 12.9 118 CH ch ₃ ch ₃ nC ₃ H ₇ COOH 79.6 60.6 7.3 12.8 59.2 7.0 12.8 119 CH ch ₃ ch ₃ NCI ^ Hg COOH 65.2 60.5 7.5 11.8 60.5 7.4 11.8 120 CH ch ₃ ch ₃ tC ₄ H ₉ COOH 168, ΟΙ 68.5 60.5 7.5 11.8 59.9 7.3 11.4

HU 207 644 Β

Example- song THE R ¹ R ² R ³ R ⁴ Op. (° C) Elemental Analysis (Calculated, Found) C H N 121 CH ch ₃ ch ₃ ch ₂ c ₆ h ₅ co ₂ ch ₃ 71.0 to 72.5 67.1 6.3 9.8 67.4 6.3 10.0 122 CH ch ₃ ch ₃ CO ₂ C ₂ H ₅ co ₂ c ₂ h ₅ oil 55.3 6.4 9.9 55.4 6.5 9.7 123 CH ch ₃ ch ₃ COOH (dihydrate) COOH 231.2 41.2 5.3 10.7 40.2 4.9 10.8 124 CH ch ₃ ch ₃ ch ₂ c ₆ h ₅ COOH 206.0 66.2 5.9 10.3 65.5 5.9 10.3 125 CH ch ₃ ch ₃ IIC4H9 co ₂ c ₂ H ₅ oil 63.1 8.3 10.5 63.6 8.2 10.0 126 CH ch ₃ ch ₃ nC ₃ H ₇ CO ₂ C ₂ Hj oil 61.9 8.0 11.1 62.2 8.0 10.4 127 CH and ₃ cl iC ₃ H ₇ co ₂ ch ₃ oil 48.1 5.5 10.2 48.0 5.4 10.0 128 CH and ₃ sch ₃ íc ₃ h ₇ co ₂ ch ₃ oil 50.3 6.3 9.8 49.9 6.3 9.6 129 CH and ₃ n (ch ₃ ) ₂ C ₃ H ₇ co ₂ ch ₃ oil 55.1 7.4 14.8 55.9 7.9 13.8 130 CH and ₃ nhch ₃ C ₃ H ₇ co ₂ ch ₃ 100.5 53.5 7.1 15.6 54.1 7.4 15.7 131 CH and ₃ ch ₃ C ₃ H ₇ co ₂ ch ₃ oil 56.7 7.1 11.0 56.9 7.5 10.9 132 CH and ₃ cl ch ₂ c ₆ h ₅ co ₂ ch ₃ oil 55.8 4.7 8.7 - - - 133 CH and ₃ cl ch ₂ c ₆ h ₅ co ₂ c ₂ h ₅ oil 57.1 5.1 8.3 57.3 5.2 8.4 134 CH and ₃ sch ₃ ch ₂ c ₆ h ₅ co ₂ ch ₃ oil 57.5 5.4 8.4 57.2 5.4 8.4 135 CH and ₃ N (CH ₃ ) ₂ ch ₂ c ₆ h ₅ co ₂ ch ₃ 90.9 61.6 6.3 12.7 62.2 6.4 12.9 136 CH and ₃ nhch ₃ ch ₂ c ₆ h ₅ 'co ₂ ch ₃ 80.0 60.6 6.0 13.3 61.0 6.0 13.2 137 CH and ₃ ch ₃ ch ₂ c ₆ h ₅ co ₂ ch ₃ oil 63.6 6.0 9.3 63.4 6.2 9.4 138 CH and ₃ oc ₂ h ₅ ch ₂ c ₆ h ₅ co ₂ c ₂ h ₅ oil 62.4 6.4 8.1 62.7 6.7 8.4 139 CH oc ₂ h ₅ cl ch ₂ c ₆ h ₅ CO ₂ C ₂ H _s oil 58.2 5.4 8.0 - - - 140 CH and ₃ cl ÍC4H9 co ₂ ch ₃ oil 49.9 5.9 9.7 49.8 5.8 9.5 141 CH and ₃ cl ÍC4H9 COOH, 84.8 48.1 5.5 10.2 47.8 5.5 10.6

HU 207 644 Β

Example- song THE R ¹ R ² R ³ R ⁴ Op. CC) Elemental Analysis (Calculated, Found) C H N 142 CH OCH ₃ cl I1C4H9 co ₂ c ₂ h ₅ oil 51.6 6.3 9.3 51.9 6.3 9.2 143 CH and ₃ cl I1C4H9 COOH 100.4 48.1 5.5 10.2 48.5 5.5 10.3 144 CH and ₃ cl ÍC3H7 COOH 133.3 46.1 5.0 10.8 46.5 5.1 10.7 145 CH and ₃ cl tC ^ Hg co ₂ ch ₃ 66.1 49.9 5.9 9.7 50.3 6.0 9.9 146 N and ₃ cl ÍC3H7 co ₂ ch ₃ oil 43.6 5.1 15.2 43.8 5.0 15.0 147 N and ₃ sch ₃ íc ₃ h ₇ co ₂ ch ₃ oil 46.0 5.9 14.6 46.3 6.0 14.3 148 CH and ₃ N (CH ₃ ) ₂ íc ₃ h ₇ co ₂ ch ₃ oil 50.7 7.0 19.7 51.5 7.1 19.5 149 N and ₃ nhch ₃ íc ₃ h ₇ co ₂ ch ₃ 91.5 48.9 6.7 20.7 48.9 6.6 21.0 150 N and ₃ ch ₃ C ₃ H ₇ co ₂ ch ₃ oil 51.8 6.7 16.5 52.3 6.7 15.9 151 N and ₃ and ₃ nC ₄ H ₉ co ₂ ch ₃ oil 50.5 6.7 14.7 51.7 6.8 12.3 152 N and ₃ and ₃ SC4H9 co ₂ ch ₃ oil 50.5 6.7 14.7 50.4 6.7 12.0 153 N and ₃ and ₃ ÍC4H9 co ₂ ch ₃ 68.0 50.5 6.7 14.7 50.4 6.8 14.9 154 N and ₃ ch ₃ ch ₂ c ₆ h ₅ co ₂ ch ₃ oil 59.4 5.6 13.9 59.5 5.7 13.4 155 N and ₃ and ₃ íc ₃ h ₇ co ₂ ch ₂ c ₆ h ₅ 84.9 58.8 6.1 12.1 58.0 6.4 12.1 156 N and ₃ and ₃ nC ₄ H ₉ co ₂ ch ₂ c _he h ₅ 59.5 59.8 6.4 11.6 59.6 6.6 11.8 157 N and ₃ and ₃ 1C4H9 co ₂ ch ₂ c ₆ h ₅ 60.2 59.9 6.4 11.6 59.4 6.7 11.7 158 N and ₃ and ₃ tC ₄ H ₉ CO ₂ CH ₂ C ₆ Hj 76.5 59.7 6.6 11.6 59.3 6.4 12.1 159 N and ₃ and ₃ íc ₃ h ₇ COOH 115.8 46.7 5.8 16.3 46.5 5.9 16.4 160 N and ₃ and ₃ I1C4H9 COOH 82.9 48.7 6.3 15.5 48.4 6.2 14.9 361 N and ₃ and ₃ 1C4H9 COOH 90.7 48.7 6.3 15.5 48.5 6.2 15.4 162 N and ₃ and ₃ tC ₄ H ₉ COOH, 131.6 48.7 6.3 15.5 49.2 6.3 15.3

HU 207 644 Β

Example- song THE R ¹ R ² R ³ R ⁴ Op. (° C) Elemental Analysis (Calculated, Found) C H N 163 N and ₃ N (CH ₃ ) ₂ iC ₃ H ₇ CO ₂ CH ₂ C ₆ H ₅ 60.0 6.7 15.6 60.0 6.7 15.5

Example 164

Methyl 2- (4,6-Dimethoxy-pyrimidin-2-yl) -oxybut-2-10 enoate

0.8 g (6.9 mmol) of methyl 2-hydroxybut-3-enoate,

A mixture of 1.50 g (6.9 mmol) of 4,6-dimethoxy-2-methanesulfonylpyrimidine and 1.04 g (7.6 mmol) of calcium carbonate in 100 ml of methyl ethyl ketone was refluxed for 12 hours. boil. The reaction mixture was filtered and the filtrate evaporated in vacuo. Purification by flash chromatography on silica gel with 1.5% methanol in chloroform.

1.37 g (78%) of the title compound are obtained. Melting point: 71.0 ° C.

ANALYSIS:

H, 5.5%; N, 11.0%. Found: C, 50.6; H, 5.8; N, 10.5%.

NMR data confirmed the title derivative.

165-168. examples

The following compounds of formula Ib can be prepared according to Example 164.

IA. spreadsheet

Example- song THE R ¹ R ² R4 9 RIO Op. (° C) Elemental Analysis (Calculated, Found) C Η N 165 CH ch ₃ ch ₃ CO ₂ CH ₃ H ch ₃ oil (boiling point 100-110 ° C / 2.0 mmHg) 59.5 6.3 12.6 58.2 6.4 12.5 166 CH ch ₃ ch ₃ COOH H ch ₃ - 57.7 5.8 13.5 57.4 5.9 12.8 167 CH and ₃ ch ₃ COOH H ch ₃ 122.0 50.0 5.0 11.7 50.2 5.3 11.3 168 N and ₃ and ₃ CO ₂ CH ₃ H ch ₃ oil 47.1 5.1 16.5 48.3 5.5 16.3

Example 169

Testing for herbicidal activity

The following plants were tested for herbicidal activity of the new active substances: maize (Zea mays, Mz); rice (Oryza sativa, R); Cocksfoot (Echinochloa crusgalli, BG); zab (Avena sativa, O); len (Linum usitatissimum, L); mustard (Sinapsis alba, M); sugar beet (Beta vulgaris, SB) and soybean (Glycine max, S).

The tests were performed with pre- and post-emergent treatment. During pre-emergence treatment, the liquid formulation of the test drug was sprayed onto the soil, in which the seeds of the test plant were pre-planted. During post-emergence treatment, the soil is watered or the plant is sprayed. During soil irrigation, the soil in which the test plants develop is irrigated with the liquid formulation of the active ingredient while spraying the formulation onto the plant.

Agricultural peat treated as soil is used in the tests.

The active ingredient is dissolved in 0.4% by weight of alkylphenol / ethylene oxide condensate (triton X-155) in acetone to form a composition for treatment. The solution is diluted with water and the resulting composition is sprayed at a rate of 1 to 5 kg / ha at 600 l / ha and irrigated at 3,000 l / ha at 10 kg / ha.

Untreated screened soil in the pre-emergence test and untreated soil containing the test plant were used as controls.

The herbicidal activity of the test compounds was evaluated visually on day 12 after spraying and on days 1-3 after irrigation and expressed on a scale of 0-9. Within this, 0 means development equivalent to control, 9 means complete destruction. An increase of 1 unit within the scale represents an increase of about 10%.

The measurement results are shown in Π. where the test compounds are designated by the number of the preparation example, the absence of a measurement result is zero, and the asterisk indicates the absence of result.

HU 207 644 Β

II. spreadsheet

authorities material example- number Watering the soil dosage zis Spraying Pre-emergence Mz R BG 0 L M SB S kg / ha Mz R BG 0 L M SB S Mz R BG 0 L M SB S ' 1 7 8 7 5 7 3 5 3 8 5 8 4 3 8 8 7 8 4 1 6 3 7 2 5 5 4 3 2 2 3 8 8 7 4 8 7 5 6 8 6 4 8 5 2 9 8 7 4 8 6 1 5 8 5 7 1 8 8 6 7 2 3 8 7 8 7 7 9 9 8 5 5 5 8 5 8 9 9 8 8 8 8 7 8 8 8 8 1 1 8 2 7 9 8 7 5 6 8 4 4 8 8 7 4 7 6 8 5 8 8 9 7 5 7 5 8 5 8 9 9 7 6 8 8 5 6 8 8 7 1 2 2 7 1 8 8 7 4 6 5 7 4 5 7 7 8 7 6 7 5 4 5 7 7 8 7 7 8 5 5 9 9 8 7 7 8 4 4 1 6 5 8 6 7 8 5 3 8 9 8 5 4 6 1 6 7 7 6 7 1 5 4 5 6 5 7 7 5 7 6 4 5 8 7 6 2 5 2 1 5 5 7 6 3 7 5 1 3 6 5 4 1 7 3 5 5 1 4 8 4 5 3 2 1 9 8 8 7 8 2 8 8 2 5 8 7 8 8 9 9 4 7 9 8 8 8 8 2 1 6 7 7 8 8 8 3 3 8 7 8 7 8 10 7 7 7 6 6 8 9 3 5 7 6 8 6 2 8 9 6 8 9 8 7 7 7 8 2 1 7 5 7 5 8 8 5 7 9 8 7 7 7 7 11 7 7 6 7 3 7 7 5 6 7 8 7 5 8 6 5 7 8 8 7 4 5 5 2 1 1 4 6 4 2 6 3 5 6 5 4 2 2 12 7 6 7 6 3 5 5 7 6 7 7 6 8 8 4 6 7 8 7 2 4 4 1 3 5 6 7 4 7 4 1 2 4 5 3 1 13 6 5 1 4 8 2 2 7 1 1 7 1 4 14 5 3 4 1 1 1 15 3 4 5 4 3 6 3 5 6 4 6 5 8 4 1 6 4 4 6 3 18 5 5 5 Φ 1 2 19 5 7 7 2 1 5 5 20 7 8 8 7 5 5 7 4 5 7 8 8 7 7 7 8 8 7 9 8 6 6 5 8 5 1 7 7 8 7 5 7 8 7 4 7 8 5 4 4 6 4 21 6 6 6 7 2 4 4 5 4 7 8 7 3 6 7 4 4 6 4 3 2 4 2 1 3 3 7 7 5 4 2 3 2 2 22 8 7 8 7 7 8 9 3 5 7 7 8 7 7 8 8 8 8 9 8 7 7 7 8 8 1 6 6 7 7 7 7 '7th 6 6 7 6 5 6 6 6 8

HU 207 644 Β

authorities material example- number Watering the soil dosage zis Spraying Pre-emergence Mz R BG 0 L M SB S kg / ha Mz R BG 0 L M SB S Mz R BG 0 L M SB S 24 7 4 6 5 3 2 5 7 7 7 7 7 8 7 5 5 7 7 7 6 4 5 2, 1 6 5 2 7 7 4 6 2 2 2 2 4 4 3 1 25 2 2 5 3 2 7 5 4 2 3 3 1 1 3 2 2 2 26 2 4 5 2 3 7 8 3 3 2 3 3 1 2 4 6 2 2 27 8 6 8 8 7 8 8 7 5 8 7 8 8 8 9 8 7 7 . * 8 7 5 7 8 3 1 6 6 8 7 7 9 7 7 4 * 8 4 3 7 5 1 28 7 6 7 5 2 7 8 4 5 2 7 2 4 7 5 2 3 4 2 * 1 6 2 2 3 29 6 4 8 3 3 7 8 4 5 2 8 2 7 8 8 7 5 6 8 * 4 7 7 3 1 1 8 1 5 8 8 6 3 3 8 1 6 5 30 7 4 8 5 2 8 7 5 5 5 5 7 5 4 9 8 7 4 * 8 3 7 8 4 1 2 3 7 2 1 8 7 6 1 4 7 6 7 1 31 * * * * * * * - * 5 3 4 7 4 5 6 7 4 6 6 7 4 6 7 7 3 1 1 1 6 2 4 5 6 4 2 6 1 2 5 5 32 7 7 7 6 5 8 7 5 5 7 6 6 4 3 8 9 6 7 8 9 6 7 7 8 8 1 3 4 6 3 1 8 7 5 5 6 8 4 3 7 7 7 33 6 6 6 4 6 5 6 3 5 3 6 2 6 7 8 5 4 5 7 3 4 5 7 2 1 2 5 1 5 6 6 3 3 3 6 1 3 3 6 34 7 7 7 6 4 8 8 4 5 5 6 6 5 4 8 8 6 6 7 8 3 4 7 7 7 1 4 2 5 3 2 8 8 5 6 6 8 1 2 7 7 6 35 7 4 7 7 6 8 8 4 5 6 6 7 7 5 8 9 6 8 9 8 7 3 6 8 4 1 6 5 7 7 8 7 5 4 9 7 7 5 6 2 36 3 3 2 2 3 5 2 4 6 4 3 7 5 4 5 4 1 1 3 1 2 2 37 7 7 8 7 7 9 8 6 5 5 5 8 6 7 8 8 7 7 8 8 7 7 7 7 7 1 1 7 2 5 6 7 4 5 6 7 4 3 7 7 2 38 5 5 6 5 7 7 5 3 4 8 7 3 7 7 3 5 9 7 5 3 3 3 1 2 3 5 5 1 2 7 4 2 1 1 39 4 5 2 4 1 1 40 4 5 6 4 2 3 5 4 6 7 7 3 8 5 5 4 7 6 4 5 4 2 1 1 3 4 5 1 6 2 1 1 2 2 1 5 3 42 5 7 2 1 3 1 43 6 7 7 1 7 1 5 5 8 7 1 8 3 3 7 7 6 6 1 1 4 3 7 1 1 2 2 3 44 7 7 7 8 1 5 7 8 7 1 8 4 3 8 7 7 7 2 1 5 5 4 7 6 3 4 4 45 7 7 8 7 7 8 9 7 5 7 7 8 7 4 8 <8 7 8 9 8 8 7 7 8 4 1 6 6 8 6 1 8 8 5 6 9 8 7 4 7 8

HU 207 644 Β

authorities material example- number Watering the soil dosage zis Spraying Pre-emergence Mz R BG 0 L M SB S kg / ha Mz R BG SHE L M SB S Mz R BG SHE L M SB S 46 8 7 8 7 7 8 9 7 5 7 7 8 7 3 8 8 7 8 9 9 7 7 7 8 ⁴ . 1 6 6 7 7 1 8 7 5 7 9 8 7 6 _? 7 47 5 6 8 7 6 8 8 5 4 4 8 4 1 7 7 3 4 8 8 6 7 6 2 1 2 2 5 3 5 4 7 7 2 6 2 48 7 7 8 7 6 8 8 5 3 6 8 6 7 5 5 9 8 6 2 7 7 1 1 5 6 4 7 2 1 8 8 5 7 4 49 6 7 8 7 5 8 7 4 5 6 6 8 7 6 8 8 7 6 9 9 7 5 7 7 7 1 3 2 7 7 4 8 6 5 2 9 8 7 2 7 4 50 4 5 7 7 3 8 7 3 5 2 8 7 3 8 5 4 3 8 8 7 2 7 4 2 1 7 6 7 4 1 1 7 4 4 7 1 51 7 7 8 7 5 8 8 2 5 6 6 8 7 4 8 8 7 6 9 9 7 5 7 8 2 1 5 4 8 6 8 7 5 2 9 9 7 2 7 7 52 3 2 4 2 3 2 4 5 4 6 3 4 6 3 4 1 1 2 1 3 1 53 7 7 8 7 6 7 ⁷ 4 5 7 7 8 6 7 8 8 7 7 9 8 8 8 7 7 8 1 5 5 8 4 6 7 5 5 5 8 8 7 4 6 6 8 54 8 8 9 8 8 9 9 7 5 7 7 8 8 7 9 8 8 9 9 9 8 9 7 8 8 1 7 7 8 8 6 8 8 8 9 9 9 8 8 7 8 8 55 7 8 8 7 7 8 9 7 5 6 6 8 6 7 9 8 8 8 9 9 7 6 6 8 8 1 5 4 7 6 5 7 8 7 6 8 8 6 4 6 8 5 56 7 7 8 7 7 8 8 8 5 7 5 8 7 7 8 8 8 9 9 9 8 9 7 8 8 1 6 4 8 6 7 7 7 8 9 9 9 7 7 7 7 7 57 7 7 8 7 7 8 8 7 5 7 5 8 7 7 7 8 7 8 9 9 8 8 7 8 8 1 5 4 8 6 6 6 7 5 7 8 8 7 7 7 8 8 58 9 8 9 8 8 9 8 8 5 8 7 8 8 7 9 9 8 9 9 8 8 8 8 8 8 1 8 7 8 7 7 9 9 8 8 9 8 8 8 8 8 8 59 8 7 8 8 7 8 8 8 5 7 7 9 8 7 9 8 8 9 9 9 8 9 7 9 8 1 7 7 8 7 7 8 7 8 9 9 9 8 8 7 8 6 60 7 7 8 7 7 8 8 7 5 7 6 7 6 7 8 8 7 8 9 9 7 8 8 8 8 1 7 6 7 6 7 8 7 7 8 9 9 7 8 8 8 8 61 7 7 8 7 6 8 8 6 5 7 6 8 8 7 8 8 7 9 9 9 7 9 7 8 8 1 6 6 6 6 7 8 7 7 8 9 8 7 7 7 7 8 62 6 6 8 7 6 8 8 8 5 7 6 7 7 7 7 7 7 7 9 9 8 7 7 7 8 1 3 4 7 7 6 7 6 7 6 9 8 8 5 7 7 8 65 6 6 7 7 5 5 5 5 8 7 3 6 3 3 5 8 6 5 4 2 1 3 5 3 4 2 2 3 2 3 66 7 6 7 7 3 7 7 2 5 5 5 7 6 6 7 8 8 8 9 8 7 7 7 8 1 2 4 7 6 2 7 6 5 5 8 8 6 3 6 6 67 7 6 7 7 4 7 4 5 7 6 7 6 7 8 5 6 8 9 8 7 3 6 3 1 5 6 7 6 5 7 4 4 5 9 7 5 4 1 68 7 7 7 7 8 8 8 8 5 7 6 8 7 7 9 , 8 7 9 9 9 8 9 7 8 8 1 7 5 8 6 7 9 7th 7 9 9 9 8 9 7 8 8

HU 207 644 Β

authorities material example- number Watering the soil dosage zis Spraying Pre-emergence Mz R BG 0 L M SB S kg / ha Mz R BG 0 L M SB S Mz R BG 0 L M SB S 69 7 6 8 7 7 8 8 6 5 7 6 8 6 7 8 8 8 8 9 9 7 7 6 8 8 _t 1 7 4 6 6 7 8 8 8 5 9 9 7 7 6 8 8 70 7 6 8 7 7 8 9 6 5 6 6 8 6 7 8 7 8 9 9 9 7 9 7 8 8 1 5 5 7 6 7 8 7 8 7 9 9 7 6 6 8 8 71 3 5 2 3 4 2 5 1 1 2 72 4 3 5 2 5 1 2 73 5 5 2 7 6 5 5 2 6 6 7 2 .7 6 5 2 3 2 4 2 3 3 1 1 3 3 6 4 4 3 1 1 1 74 3 5 5 2 4 3 9 4 7 1 1 8 4 75 5 7 7 7 2 5 4 5 5 6 7 7 5 7 6 3 6 8 7 5 2 6 2 1 4 4 7 6 3 7 4 1 4 7 6 4 4 76 7 6 5 7 6 3 1 5 5 4 7 6 5 7 7 4 5 ' 9 7 7 3 5 2 1 4 3 6 6 3 6 4 1 3 6 4 5 4 77 5 3 4 4 4 4 3 4 5 7 7 1 1 2 1 2 5 7 78 8 7 8 8 7 8 8 7 5 8 7 8 8 8 8 8 8 9 9 9 9 9 7 8 8 1 7 7 8 8 7 8 8 8 8 9 9 8 7 7 8 7 79 8 7 9 8 9 9 8 7 5 7 7 8 8 7 8 8 7 9 9 9 9 9 8 8 8 1 6 7 7 8 7 7 8 7 9 9 9 9 8 8 8 8 80 7 7 8 7 7 8 7 7 5 5 6 7 7 7 8 8 6 8 9 8 8 8 7 7 8 1 3 5 4 6 7 8 7 5 7 8 8 7 8 7 7 5 81 7 7 8 8 7 8 8 7 5 7 6 8 7 8 8 8 8 9 9 9 8 8 7 8 7 1 7 6 7 7 8 8 8 7 8 9 9 8 8 7 8 7 82 7 7 8 7 7 8 6 7 5 8 6 8 7 7 7 8 7 9 9 9 7 8 7 8 8 1 6 6 7 7 7 7 8 7 6 9 9 7 6 7 7 7 83 7 7 8 7 6 7 7 6 5 8 6 8 8 7 8 8 8 8 9 9 7 6 6 8 8 1 7 6 7 7 7 7 7 7 8 9 9 7 6 6 7 7 84 4 5 2 2 5 3 2 2 1 1 3 85 2 6 8 4 5 8 8 3 5 4 7 3 3 8 7 7 8 4 6 7 8 2 1 1 6 1 1 6 7 6 6 2 6 7 86 5 Ί 7 7 3 7 6 3 5 6 7 7 7 4 7 7 6 7 8 8 6 6 6 8 2 1 3 6 5 5 5 6 3 3 5 6 4 2 6 5 1 87 7 7 2 5 4 2 2 5 6 6 7 6 6 6 6 6 3 8 4 3 2 2 1 2 2 5 4 4 4 4 3 4 1 88 5 2 3 4 6 5 1 1 2 3 6 3 89 3 6 3 2 3 6 5 3 5 3 6 7 6 5 7 7 3 3 5 6 4 2 6 5 1 2 5 6 5 5 6 5 2 1 3 5 2 3 2

HU 207 644 Β 2

authorities material example- number Watering the soil dosage zis Spraying Pre-emergence Mz R BG 0 L M SB S kg / ha Mz R BG 0 L M SB S Mz R BG 0 L M SB s 90 7 7 8 7 7 8 8 7 5 7 7 8 7 7 8 8 8 9 9 9 7 8 7 8 7 3 7 6 7 7 7 7 8 8 8 8 9 7 6 7 8 7 91 7 7 8 7 7 8 8 7 5 7 7 8 8 7 8 8 8 9 9 9 8 9 7 8 7 1 7 6 8 7 7 8 8 8 9 9 9 7 8 7 8 7 92 7 7 8 7 6 7 8 7 5 7 7 8 7 6 7 7 8 8 * 8 7 6 7 7 3 1 7 7 7 7 6 7 7 8 6 8 6 4 7 7 3 93 7 7 8 7 6 8 8 7 5 7 6 8 6 7 8 8 8 8 9 9 7 8 7 8 7 1 4 6 7 6 7 7 8 8 8 9 9 6 6 7 7 4 94 8 8 8 8 7 8 8 6 5 7 8 9 8 8 8 8 8 9 9 9 8 8 7 7 7 1 7 8 8 7 7 8 8 8 8 9 9 8 8 7 7 7 95 8 8 8 9 7 8 9 7 5 7 8 8 8 7 8 9 9 9 9 9 7 7 8 7 4 1 7 8 8 8 7 8 8 8 8 9 9 7 7 7 7 3 96 8 8 8 ⁸ 7 8 9 7 5 7 8 9 7 7 8 8 8 8 9 9 8 8 7 7 7 1 7 7 8 7 7 7 8 8 8 9 9 7 7 7 7 7 97 8 8 8 7 6 7 8 7 5 8 8 8 8 7 8 9 8 7 8 8 8 7 7 7 5 1 6 7 8 7 7 7 8 8 5 8 8 7 7 7 7 4 98 7 8 8 7 7 7 8 8 5 7 8 8 7 7 7 8 7 3 8 8 6 3 7 5 2 1 7 8 8 7 7 7 8 7 2 7 8 6 2 6 5 2 99 7 7 7 6 5 7 7 7 5 7 8 7 7 7 7 7 7 4 8 8 7 5 6 5 * 1 4 7 7 6 7 6 6 6 2 8 8 6 2 3 4 100 6 7 7 6 4 7 8 8 5 7 8 8 7 7 7 8 7 4 8 8 7 2 4 7 2 1 5 6 8 7 6 7 8 5 2 7 8 6 1 2 4 101 7 7 8 6 7 7 8 8 5 7 7 8 7 7 8 9 8 8 9 9 7 7 7 7 7 1 6 7 8 6 7 7 8 8 8 8 7 6 3 6 6 7 102 7 7 8 7 7 7 8 7 5 7 7 8 7 7 8 8 8 8 9 9 7 8 7 7 7 1 7 7 8 6 7 7 8 8 7 9 8 7 5 6 6 7 103 7 7 7 6 6 7 8 7 5 7 7 8 7 6 8 8 8 8 9 9 7 7 7 8 7 1 7 7 7 7 6 6 8 7 8 9 9 7 7 7 7 7 104 7 7 8 7 6 7 8 8 5 7 7 8 7 6 8 8 8 8 9 9 7 6 7 8 8 1 3 7 6 6 7 8 8 8 9 9 7 4 7 8 7 105 5 7 7 6 4 6 6 6 5 7 7 8 7 6 7 8 7 4 7 7 4 4 5 4 1 7 7 8 7 6 7 7 7 3 7 7 3 3 4 3 106 6 7 8 7 6 7 7 7 5 8 7 8 7 6 7 8 8 7 8 8 7 4 7 6 4 1 7 7 8 7 6 7 8 7 7 8 7 4 3 5 6 2 107 7 8 8 8 6 7 7 7 5 7 7 8 7 6 7 8 7 8 9 9 7 6 7 7 5 1 5 3 2 3 3 2 4 7 8 7 4 7 5 108 7 7 8 7 7 7 7 7 5 7 7 8 6 6 8 8 6 8 9 9 8 8 7 8 7 1 5 6 7 6 6 7 7 6 8 9 8 7 6 7 8 6 109 7 7 8 7 6 7 7 6 5 8 7 8 7 6 7 8 7 8 9 9 7 5 7 7 3 1 7 7 8 6 6 7 7 7 7 8 8 5 3 7 7 3 111 5 5 3 4 3 2 5 4 6 7 7 7th 6 5 6 5 4 4 3 3 1 2 / 5: 4 4 6 4 2 1 1 1

HU 207 644 Β

authorities material example- number Watering the soil dosage zis Spraying Pre-emergence Mz R BG 0 L M SB S kg / ha Mz R BG 0 L M SB S Mz R BG 0 L M SB S 112 7 8 8 6 6 7 8 8 5 7 7 7 7 7 8 8 7 6 8 9 6 5 6 6 3 1 6 7 7 7 7 7 8 7 4 8 9 6 4 5 6 113 7 8 8 7 7 8 8 7 5 7 7 8 7 7 8 9 7 9 8 8 7 3 6 6 1 7 7 8 7 6 8 8 7 7 5 8 5 1 6 5 114 6 7 7 7 6 7 8 7 5 6 6 7 6 6 7 7 7 6 6 6 5 2 5 4 4 1 5 5 7 6 6 6 7 5 4 5 4 2 3 1 115 7 7 8 7 6 8 8 8 5 7 6 7 7 6 8 8 7 7 8 8 7 8 6 8 7 1 5 6 7 7 6 8 8 7 6 6 8 6 7 6 6 5 116 4 4 6 6 5 6 7 6 5 4 7 6 6 8 8 5 5 5 8 5 5 6 5 4 1 3 7 6 6 8 8 4 5 5 8 4 4 6 5 4 117 7 7 9 8 6 8 8 8 5 7 7 8 6 6 8 9 8 9 9 9 7 8 7 8 6 1 7 7 7 6 6 8 8 8 9 9 8 6 7 6 8 5 118 7 7 8 7 4 8 7 6 5 4 7 8 6 2 9 8 6 7 9 9 7 7 7 8 2 1 6 7 6 8 7 3 4 9 8 7 2 7 7 119 7 7 8 8 6 9 8 6 5 4 7 9 7 5 9 7 6 6 9 9 8 7 7 8 2 1 6 8 6 3 8 6 3 1 9 9 7 4 7 7 120 8 7 9 8 8 8 8 7 5 7 7 9 7 7 9 8 7 9 9 9 8 9 7 8 8 1 7 7 9 7 6 8 8 6 7 9 9 7 8 7 7 7 121 7 4 5 2 3 2 9 4 4 4 5 4 5 7 3 1 2 7 2 2 1 2 2 3 7 122 2 4 2 3 2 6 3 5 4 5 8 6 6 8 9 8 3 8 5 2 4 5 5 2 1 2 2 7 4 3 8 7 6 6 2 1 2 1 1 123 3 2 5 4 4 7 4 2 6 5 7 1 3 1 4 3 4 124 2 3 8 3 5 3 2 3 8 4 1 2 6 1 1 1 7 2 2 125 7 8 8 7 2 8 6 2 5 7 7 8 6 4 8 8 7 4 9 9 6 4 7 7 3 1 4 6 7 4 1 8 7 4 3 8 8 6 7 7 126 7 8 8 7 2 8 5 2 5 7 7 8 6 6 9 8 6 4 8 9 7 2 7 6 3 1 4 6 8 5 2 8 5 2 7 8 6 7 2 2 127 7 7 7 7 8 7 8 4 5 7 6 7 6 7 6 5 6 7 9 8 7 7 7 8 1 4 4 6 4 6 2 2 4 8 7 5 4 6 128 6 6 5 5 7 5 5 2 2 5 6 3 4 4 6 6 6 6 7 6 1 2 1 3 2 2 4 2 4 2 129 5 5 5 2 7 5 5 1 2 2 6 6 5 4 7 7 6 6 4 7 4 1 4 2 2 2 1 1 3 1 130 5 5 4 4 6 3 5 2 4 4 6 4 4 2 6 6 5 2 6 3 1 3 1 1 2 1 1 2 131 7 7 8 7 7 7 4 2 5 4 5 8 7 7 8 5 4 4 9 8 7 7 7 4 1 1 2 5 3 6 5 3 8 6 6 2 6 132 2 5 7 3 5 2 3 5 6 7 8 7 6 2 4 5 5 3 7 4 1 1 2 3 5 7 2 2 1 1 4 1

HU 207 644 Β

authorities material example- number Watering the soil dosage zis Spraying Pre-emergence Mz R BG 0 L M SB S kg / ha Mz R BG 0 L M SB S Mz R BG 0 L M SB S 133 2 7 2 5 2 2 5 7 7 8 7 5 5 4 4 7 4 1 3 5 4 6 4 3 3 1 134 5 2 3 3 5 3 2 1 3 1 1 135 4 2 5 2 7 7 4 1 1 4 2 1 13Ó 5 2 4 7 5 1 3 2 137 3 2 6 5 5 2 4 5 6 7 8 7 5 2 7 6 4 3 7 5 1 1 2 3 6 7 4 2 5 2 5 2 138 3 4 4 3 2 4 2 5 3 4 8 6 6 8 8 6 3 5 8 4 2 5 5 1 6 5 3 6 5 3 2 3 7 1 2 2 139 * * * * * * * 5 2 3 7 4 4 2 2 1 1 3 140 6 7 8 7 7 7 2 5 4 6 7 6 4 9 8 5 3 8 8 6 4 6 8 5 1 1 4 6 5 3 7 7 4 1 6 8 4 1 6 6 4 141 6 7 7 7 1 8 8 2 5 4 6 8 7 4 8 7 6 4 7 8 6 4 7 7 5 1 1 4 7 6 1 7 6 4 3 6 7 5 7 7 142 4 7 7 5 2 8 7 3 5 4 4 6 3 2 8 8 3 2 7 7 4 2 7 6 2 1 1 2 4 2 8 5 2 2 5 6 3 7 4 1 143 6 7 7 5 3 8 7 4 5 4 6 6 6 5 8 8 6 2 7 7 6 2 7 7 1 1 5 5 3 2 6 5 3 2 6 6 3 6 5 144 7 7 8 7 7 7 8 6 5 5 7 8 7 6 8 8 6 7 9 9 7 6 7 7 3 1 5 6 7 7 6 7 7 5 6 8 8 7 4 7 6 2 145 5 6 7 6 4 7 7 4 5 4 6 4 4 6 5 2 4 7 5 4 2 5 1 6 1 1 4 3 1 5 3 1 1 1 2 1 4 146 3 5 2 6 3 5 6 3 5 1 1 4 3 2 3 1 147 3 6 6 3 7 7 5 2 5 4 3 6 4 7 7 8 5 6 8 8 5 7 6 7 1 1 1 2 2 6 5 5 1 2 3 2 2 3 4 148 6 7 6 7 6 3 5 2 5 7 7 7 7 7 7 6 6 7 9 8 7 7 7 7 1 4 6 6 6 5 5 5 4 4 8 6 5 2 3 2 149 3 6 7 7 5 3 4 3 5 4 7 7 7 7 7 6 4 6 9 8 7 7 7 7 4 1 2 6 6 6 2 5 3 1 7 7 4 3 150 4 6 6 6 4 3 5 2 5 4 5 7 7 5 7 5 5 6 8 8 6 3 5 2 1 2 2 4 3 2 6 1 4 4 3 2 1 151 8 8 8 7 6 8 7 2 5 7 7 8 7 6 9 7 7 8 8 8 7 4 6 8 1 4 6 6 7 4 6 5 5 6 7 7 6 6 5 152 7 7 8 7 5 8 6 5 5 7 7 8 7 7 8 6 7 9 9 8 7 7 7 7 5 1 6 6 7 6 6 7 5 5 8 9 8 6 2 6 4 153 8 8 8 7 6 8 8 7 5 7 6 7 7 7 8 8 7 8 8 8 7 7 7 7th 8 1 3 4 7 6 7 6 6 5 6 8 6 4 7 6 2

HU 207 644 Β

authorities material example- number Watering the soil dosage zis Spraying Pre-emergence Mz R BG 0 L M SB S kg / ha Mz R BG 0 L M SB S Mz R BG 0 L M SB S 154 4 3 2 5 4 2 5 4 6 7 7 6 7 2 4 4 4 5 5 2 1 2 2 4 6 2 7 3 2 3 155 6 6 7 6 2 6 4 5 5 6 4 8 7 7 7 7 5 7 8 8 6 4 6 3 2 1 6 4 7 7 6 5 5 4 6 7 8 4 2 2 1 156 7 8 7 7 3 7 3 5 5 8 7 7 6 8 8 5 4 8 7 5 2 5 2 1 3 7 7 7 5 7 7 3 2 6 7 4 3 .2 157 7 6 7 6 2 7 6 4 5 7 3 7 7 5 8 8 7 7 8 9 7 2 7 5 3 1 4 3 7 7 2 7 6 5 6 8 8 6 5 3 2 158 6 7 6 5 4 6 8 4 5 6 6 8 6 7 7 8 5 5 Ί 7 3 2 3 4 2 1 4 5 6 6 7 6 8 4 2 5 5 2 2 3 159 7 7 7 7 3 7 4 6 5 7 7 8 7 7 8 7 6 8 8 9 7 4 7 5 3 1 4 7 7 6 6 7 5 4 6 8 8 6 1 5 2 160 7 7 7 7 4 7 4 3 5 6 7 7 6 6 8 8 5 7 8 8 6 4 7 7 2 1 3 6 6 5 4 7 5 2 4 8 6 5 1 5 3 161 6 7 8 7 8 6 2 5 6 7 8 7 5 8 8 6 7 8 9 6 3 7 6 1 2 5 7 6 2 8 5 4 5 7 7 5 6 1 162 7 7 9 7 6 8 9 8 5 7 7 9 7 6 8 8 8 8 9 9 7 8 6 7 7 1 5 7 8 7 6 8 8 6 8 9 9 7 7 6 7 6 163 3 8 7 7 3 4 5 6 7 8 7 7 7 7 5 6 8 7 3 7 1 4 5 8 6 5 6 4 2 6 3 164 2 6 2 6 5 8 5 3 3 6 5 5 7 7 7 2 4 4 2 2 8 8 2 1 1 2 2 3 5 2 2 5 5 166 5 4 1 1 167 5 4 7 3 6 8 8 2 5 6 4 7 6 7 8 8 5 5 7 7 6 6 6 8 5 1 2 5 5 3 5 7 3 2 3 3 4 168 5 2 2 3 3 2 2 2 2 2 3 1 2

PATENT CLAIMS

Claims (3)

PATENT CLAIMS CLAIMS 1. A herbicidal composition comprising as active ingredient a triazine / pyrimidine derivative of the Formula I or a salt thereof, wherein A is N or -CR ⁵ - wherein R ⁵ is H, R ¹ and R ² are each independently C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, C 1 -C 4 alkylthio or C 1 -C 4 mono or dialkylamino in alkyl, R is a radical of formula (a) wherein R ³ is hydrogen, C 1-8 alkyl, C 1-4 alkylthioalkyl, C 3-6 cycloalkyl, thienyl, C 1-2 phenylalkyl, phenyl optionally substituted with halo, (C 1 -C 4) -alkyl, (C 1 -C 4) -haloalkyl, or (C 1 -C 4) -alkoxycarbonyl, and -COR ⁵ 'wherein: R ⁵ 'is hydroxy, C 1 -C 4 alkoxy, C 1 -C 4 alkoxycarbonyl, or in its alkyl moieties C 1 -C 4 dialkylamino, R ⁴ is -COR ⁶ wherein R ⁶ is hydroxy, C 2 -C 6 alkynyloxy, C 1 -C 8 alkoxy optionally substituted with halo, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio optionally halogen, C 1-4 alkyl or C 1-4 alkoxy23 It may be substituted by a substituted phenyl group, a thienyl group, a furanyl group or a tetrahydrofuranyl group, and a C 1-4 alkylthio group, a phenylthio group, a C 1-4 dialkyliminoxy group or an amino group which may be It may be substituted by a C4 dialkylamino group or a phenyl group optionally substituted by a C1-4 alkoxycarbonyl group, a hydrazido group, or a phenoxy group optionally substituted by a nitro group, a hydroxymethyl group, a (C1-C4) alkyl group or it may be substituted with a group, or R is a group of formula (b) wherein R ⁴ 'is a carboxyl group or a C 1 -C 4 alkoxycarbonyl group, R ⁹ is hydrogen, ^{R, o} is C1-4 alkyl, with the proviso that R ¹ and / or R ² is chloro when A is a nitrogen atom, 0.5 to 95% by weight of solid carriers and / or liquid diluents and optionally surfactants materials. A process for the preparation of a triazine / pyrimidine derivative of formula (I) and salts thereof, wherein A is nitrogen or -CR ⁵ - wherein R ⁵ is hydrogen, R ¹ and R ² are each independently C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, C 1 -C 4 alkylthio or C 1 -C 4 mono- or dialkylamino in alkyl; R is a group of formula (a) wherein R ³ is hydrogen, C 1-8 alkyl, C 1-4 alkylthioalkyl in its alkyl moieties, C 3 -C 6 cycloalkyl, thienyl, C 1 -C 2 phenylalkyl, phenyl optionally substituted by halo, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, or C 1 -C 4 alkoxycarbonyl and -COR ⁵ 'wherein R ⁵ 'is hydroxy, C 1 -C 4 alkoxy, C 1 -C 4 alkoxycarbonyl or C 1 -C 4 dialkylamino in alkyl; R ⁴ is -COR ⁶ wherein R ⁶ is hydroxy, C 2 -C 6 alkynyloxy, C 1 -C 8 alkoxy optionally substituted with halo, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio optionally substituted by halogen, C 1-4 alkyl or C 1-4 alkoxy substituted phenyl, thienyl, furanyl or tetrahydrofuranyl, and C 1-4 alkylthio, phenylthio, in the alkyl moieties thereof. a C1-C4 dialkyliminoxy group or an amino group optionally substituted by a C1-C4 dialkylamino group or a phenyl group optionally substituted by a C1-C4 alkoxycarbonyl group, a hydrazido group or a phenoxy group optionally substituted by a nitro group, a hydroxy group; methyl, C 1 -C 4 alkyl or group (c) may be, or R is a group of formula (b) wherein R ⁴ 'is a carboxyl group or a C 1 -C 4 alkoxycarbonyl group, R ⁹ is hydrogen, R ¹⁰ is C 1 -C 4 alkyl, with the proviso that R ¹ and / or R ² is different from chlorine when A is nitrogen, a) a compound of formula II wherein: R ^1, R ² and A are as defined above, L is a leaving group, and is reacted with a compound of formula (IH) R ³ and R ⁴ are as defined above or R ³ is = CR ⁹ R ¹⁰ - wherein R ⁹ and R ¹⁰ are as defined above or b) A is -CR ⁵ - preparation of the compounds of formula (I) containing a group of formula (IV) compound, wherein ^R! R ² and R ⁵ are as defined above, a quinolinedine (V) with, wherein R ³ and R ⁴ are as defined above or R ³ is = CR ⁹ R ¹⁰ wherein R ⁹ and R ¹⁰ are as defined above. Optionally X is a leaving group and the resulting compound of formula (I) into another (I), a compound of formula in which R ¹ and / or R ² is a halogen-containing compound known as ^R! and / or R ² is hydrogen, C 1 -C 4 alkylthio or C 1 -C 4 mono- or dialkylamino in alkyl, or R ⁴ or R ⁴ 'is ester group in a known manner R ⁴ and R ⁴ 'to form a compound having a carboxyl group, or converting the carboxylic acid of formula (I) salt or converting a carboxylic acid of formula (I), a salt into the free acid or into another salt.